Process of nitration.



v i; 1 l l N it it. real i WT; air I EMMET F. HITCH, OF ALTON, ILLINQIS,ASSIGNOR 'IO EQUITABLE PGWDER MANUFAC- TURING COMPANY, OF EAST ALTON,ILLINOIS, A CORPORATION OF NEW JERSEY.

PRGCESS F NITRATION.

imLvAnmlm 1 198 1 29 Specification of Letters Patent.

No Drawing.

To 1. 77 whom if may r-(UU'M'IZ Applic ed April 17,

Patented Sept. 12, 19145..

191.5. Serial Ho. 22,135,

chlorate, such as chlorate or potash Or Be it. known that l, Earner lnixxcis" chlorate of soda, for instance although 55 lll'rcn, a citizenof the llnited t itatcs. reywr sc a raluahle oxidant in making mixedsiding at Alton. in the county of Madison explosives is of restricteduse since it is not 5 and State of Illinois, have invented certain safein dry compositions while with most new and useful improvements inProcesses oily materials too much oil must be used of h itration, ofwhich the following is a in order to utilize the oxygen of the chlosospecllication. rate; that is the quantity of oil necessary Thisinvention relates to processes of is too great for a uniform, easilyhandled it) nitration; and it comprises a method of mass.

nitration particularly adapted to aromatic The best materials for thestatedpurposes hydrocarbons containing one ormore methyl are the nitroderivatives of the aromatic 55 groups and to their mixtures but alsoappli' hydrocarbons or the phenols; the nitro decable to the nitrationgenerally of organic rivatives of henzol, toluol, (methyl-benbodies, andparticularly where it is desired Zeno), the xylols, naphthalene,anthracene, to cause an entrance of two or more nitro phenol, thecresols, etc, since they are stable groups at the same time, whereinsuch inabodies of good explosive power; but unfor- 7o terial in a fluidstate is admixed with a powt-unatcly when nitrated to a high degreedered solid nitrate, which is best sodium these materials mostly furnishsolid bodies, nitrate and the mixture is then treated with or substancescrystallizing readily at moda slight excess above the theoreticalquanerately low temperatures. The lower nitrau tity of sulfuric acid,the amount of nitrate tion products, such as the mononitro coniso usedcorresponding (with slight excess) pounds, are often, but not always,fluid; the to the number of nitro groups it is desired dinitro compoundsare mostly solids but 25 to introduce; all as more fully hereinafternearly all the trinitro compounds-are solid 1 set forth and as claimed,and have a relatively high melting point.

i In the explosive industry. there is a de- The higher nitrationproducts are also mand for explosive materials which shall somewhatexpensive to make by the usual he of a high degree of nitration (thatis, methods since their production usually re- 30 containing as manychemically combined es a double nitration; as by nitrating NO "maps inthe molecule as po ble) and nitric acid and suliisequently with shallalso be liquid or soft and fluent. They re of itric acid and sulfuricacid. should he substantially non-volatileat ordillith toluene (toluol)the inononitro prodnary temperatures. High nitration is de acts arefluid and the dinitro and trinitro 35. Sirable as increasing theexplosive power; products are solids ordinary temperatures liquidity orsoftness in nitratel productsis when in a state of purity. To makemadesirable for many-purposes. For example terials from toluenecontaining any great, in making gela'tiuized explosives (such as amountof trinitr-o compounds ordinarily gun-cotton made into a gelatinous masswith requires. a double nitration with intermeso nitroglycerin) there isa demand for a nondiate, treatments which add to the expense.

volatile liquid material which is in itself Further, by the nitrationmethods in use'an explosive and which can be added to the excess ofnitric acid is always used and this mixture to restrain the tendency ofnitroexcess must subsequently be recovered. glycerin to freeze in coldweather. lsla- There are now in commercial use certain 45 terial of thikind is also desirable as a diliquid nitro tolucncs with a percentage'ofrect addition to nitroglycerin intended for nitrogen above thatcorresponding to dinitro use in making dynamite. In making extoluene,which are known to the tradeas plosive mixtures with the usual oxidantsor liquid trinitro toluene" 'llhese composioxygen-bearing salts,nitrates, pcrchlorates, tions are made by dissolvinggreater or less 50permanganates, chlorates and the like, such amounts of commercial solidtrinrtro toluene I a material is also desirable since it rende s inn'iixtures of inonoand di-nitro toluenes. possible the production ofplastic composi Such mixtures however are not satisfactory tions notreadily affected by moisture. A

for the stated purposes. On long standing" at moderately lowtemperatures, the trinitro toluene components tend to separate out moreor less entirely 1n granular form or to form with the'liquid nitro oilsa composition of a pasty consistency. This separation of the trinitrotoluene is due to the fact that the solutions when prepared in thismannerare supersaturated and also to the fact that some of the volatilemononitro toluenes which act as solvents escape by. evaporation on. longstanding. This volatile nature of the so-called liquid nitro toluenes isespecially objectionable when they are used ,in the. manufacture ofgelatcoal tar oils, either the light tar oils or the heavy tar oils; orboth together. Phenolic bodies may or may not be removed. The coal taroils are. composed of a large number of different hydrocarbons of thearomatic series, of benzene, methylbenzene (toluene), dimethylbenzenes(the xylols), ethylbenzene, etc., all susceptible of yielding nitroproducts of good explosive qualities. But it has heretofore been founddifficult with any of these hydrocarbons, or with the oils themselves,to produce in any simple way or by any simple operation high nitroderivatives; derivatives containing more than one nitro group. In theart where high nitrated derivatives are desired it is, as stated,customary to nitrate in two or more steps; amononitro compound being,for example, first formed and this afterward converted into di and tricompounds. For example, toluene isfirst nitrated to form a mixture ofthe three mononitro derivatives and then these mono derivatives areafterward renitrated to give the 'di and tri compounds. I havediscovered however that by the use of a special method of nitration itis possible to obtain directly these highly nitrated derivatives withoutthe stagewise procedure of the prior art; such method being applicableeither to the sep-- arate hydrocarbons, or, and advantageously for thepresent purposes, to mixtures of these hydrocarbons. In such method, in

lieu of using the ordinary direct nitration with nitric acid or with amixture of nitric and sulfuric acids Iemploy a special procedure. Tothis end, I mix the material in liquid form with a powderedsolidnitrate, 1

being, say, of such a fineness as to pass a mesh sieve. The proportionsof the material and ofnitrate will depend upon the particular degree ofnitration desired in the ultimate product as hereinafter set forth;

but in all cases the proportions of solid to liquid are such that themixture will be of a more or'less pasty'consistency, with the fluidmaterial uniformly distributed and filming the faces of the particles ofsolid" This uniform distribution of solid nitrate.

- nitrate and liquid material is an important feature in the presentprocess. To this mixtune I add sulfuric acid slowly with carefulregulation of the temperature and energetic mixing and'stirring.perature during this operation should not rise much above C. and it maybe much lower. After the full quantity of acid has been added mixing maybe continued for an hour, or thereabout. be discontinued and thematerial heated-47o thereafter the heat increased to 120 or 150, heatingat the higher temperature being continued until oxids of nitrogen ceaseto be evolved. I

In the method of operation ust described the nitric acid liberatedfromthe nitrate by the sulfuric acid is directly presented to thecompound to be nitrated as fast as formed and in a condition of maximumstrength and dryness. and complete. To all intents and purposes thematerial and the nitrate are presented simultaneously to the action ofthe sulfuric acid; this being a .very important point. in any nitrationwhere the sulfuric acid has an opportunity to act directly uponthe'material there is a tendency toward the formation ofsulfoniccompounds asin cases where tion that the nitric acid so developed inwhatmay be called a nascent condition, gives a smoother and more rapidnitration and a more uniform and higher nitration product.

Finally stirring may.

Ordinarily the tem- -about, say, C. for an hour or so and Nitration israpid theoretical masses 4 In the presentmethod the utilization of thenitric acid of. the nitrate in the formation of nitro compounds isnearly the amount, but a slight excess of nitric acid over the theorybeing required. l urtiier, .l have found that 1 can control the degreeof nitration by the amount of nitrate used; or, stated in another way,i. can at pleasure directly produce mono, di .or tri nitro compounds byusing the corresponding amounts of nitrate. In the production ofnitro-toluenes, for example, with one proportion of nitrate-ct soda Imake the mono nitro compound; with double the amount I produce a mixtureof the three dinitro bodies, and with triple the amount I can producehighly nitrated compositions .c0n-- taming the tri derivatives. I

With the aid of the described method using the complex mixtures orhydrocarbons found in coal tar oils, I can produce compositions whichare highly nitrated and the same time are permanently fluid andsubstantially non-volatile at ordinary tern peratures. This 15 for thereason that the process produces so many nitro' products from the manyhydrocarbons that their mutual influence in reducing the fusing pointmakes the final composition fluid at ordinary temperatures.

1 can also use the described process of nitration for many materials notusually presumed. to be nitratable. I have succeeded in nitratingmineral oils both those of paraiiinic nature and those of naphthenic .orquasi-aromatic nature, as Well as vegetable and animal oils and manyother liquid or readily fusible solid substances; :liquid or fusibleenough to film over the nitrate fragments at a temperature not too highfor nitration; say about 90 or 100" G. I have found that thenitrataoility 0 these other materials may be advantigeously utilized inthe specific invention herein described and claimed in that I may add amodicum of such material as rosin, rosin 0i], lubricating oil, Vaseline,kerosene or the like to the tar oils prior to nitrati-ng. Co-nitrationof these mineral oil materials with tar oils, etc., furtheriiicreasesthe complexity of the final product and to thatex tent stillfurther reduces the melting or freezing point, i

In. a specific embodiment oft-he present invention 1 may take about 100parts by. veight at light tar oil, say the fraction distilling between100 and 12O", thoroughly mix the oil in a dry condition with, say, 250

groundto (50 parts of dry nitrate of soda. mesh. should be asintnnate'as possible. To this mixture X then add 450 parts of sulfuric al: the ordinary commercial strength of 1.8% spe .v'ity serving verywell. The use of fumin sulfuric acid, or of acid enl'ncorporation ofliquid and solid-v riched WithSOE' While it may be practised, does notgive substantially better results. The addition of sulfuric acid is betrather slow and energetic stirring should beresort ed to in order toobtain with certainty the desired simultaneous contact of the sulfuricacid ith the oil and with the nitrate. Dun

ring this stage of the operation the temperature tends to rise and itshould be regulated so that it shall not go much. ahov 90 C. The precisetemperature to be used hoivever depends .in a measure upon theparticular n'iaterialstreated and the end product de; sired. Vitlrhghttar oils in making freely fluid endproducts of high nitration, about 90.C. 1s a good temperature of operation.

After all the acid is added, stirring may be continued for an hour inorder to produce completeness of reaction. Then the mixture may bewarmed untilit reaches about 100 C., at which ten'iperatureit may alsobe kept for i bout an hour. Finally the temperature maybe graduallyincreased to about 150 (3., being kept at this temperature until oxidsof nitrogen are no longer evolved. 'hen this point is reached, the lowersemi-liquid layer containing the excess of acids and sodium .bisulfa'temay be separated from the upper and to the various nitroglycerincompositions such asblasting gelatin. Used with perchlorate,chlorate ornitrate of soda or potash or mixtures thereof it will furnisht-henecessary carbon and hydrogen for the utilization. of the oxidizingenergy of these substances, forming plastic substances without giving anunhandy bulk of liquid. N or are its 'apors or fumes poisonous oroii'ensive in manufacture or use as is the case compounds andsubstantially free of'm'ononitro compounds. it complete conversion intotrinitro compounds is required. the op eration of nitration may berepeated. in nitrating toluene to produce fluid products a firstnitration temperature of around 90 desirable.

Dinitro toluene mixtures containing the, three dinitro bodies in varyingproportions maybe readily made under the described method by reducingthe amount of nitrate temperature LlbO-Ti. described, yin, around.

90 C.. the roportion of metadinitrotoluene may be .l lU ed as high 30per cent.

lnnltratingmixtures of aromatic hydrocarbons, or of ta r oils, withother hydrocarbons or oils, such as petroleum oils, in the presenti11am1eii, apparently a faugoing nitratlon of the petroleum oils may beattained when the percentage oi. petroleum oil is not" above 15 percent; that is. the nitrogen percentage of the :linished nitratedcomposition does not difier materially whether small amountsof petroleumoils are in the initial .lliXtlll'fi or not. This fact enables the useof rather impure or low grade oils or distil lates analogous in generalcharacter to the coal tar oils, such as those made in Various processesof converting petroleum oils into benzoh toluol and the like, since thepresence of residual non-aromatic or petroleum oils in small amountsdoes notinterfere with the;

process. Similarly many shale oils, brown coal tar oils, .etc., may beused, alone or in admixture with coal tar oils. Xaphthenic oils, such asare obtained from California, Texas and )lexican oils may also be usedin admixture with coal tar oils and in somewhat greater proportion thanis the. case with ordinary Vaseline or with parafl'inic oils.

1 find that mixtures containing a small. proportion of a petroleum oilor petroleum material, such as aseline, lubricating oil, etc, areadvantageous as they nitrate rather more readily and smoothly; thisbeing possibly due to the petroleum oil acting. so to speak, as acarrier of nitro groups in nitration. T he final products are alsosomewhat more fluid.

Petroleum'products while they may be nitratcd alone do not ordinarilygive end compositions which are as good alone as those obtained from taroils. However-by repeat ing the operation, more nitro groups can beintroduced and the explosive qualities raised.

For practical purposes I prefer to'ni= trate the methylated or ethylatedhydrocarbons oi the benzene series since the "nitro products yielded areherter explosives. And by using the mixture of these hydrocarbons foundin tar oils I obtain still .bet tcr products than by using the purehydrocarbons.

I regard the stated method of nitration as one of a quite generalapplicability although particularly advantageous for tar oils and theircontained hydrocarbons. It is particularly, advantageous in nitrationswhere it is desired to introduce more than one Intro The describedprocessmay also advantageously be applied to the treatment oi withpetroleum oils. Naphthalene with or per cent. of lubricating oils formsa fluid composition well suited for nitrating in the manner described.But. naphthalene alone may be melted and so treated. It is advantageoushowever in operatingwith naphtl1a= lene for the sakecf greaterfluidityof the final products, to use some tar oiliaswell as some petroleummaterial. icnthracene and anthracene oil (dead oil) may also be used.Rosin and rosin oil may also be used. Like petroleum materials theyadjuncts to the aromatic oils such as coal tar oils. Rosin may be usedin slightly larger amounts than rosin oil. I

lhe complex, highly nitra'tcd 'con1 ositions obtained by nitrating taroils in the described manner. with or without'- admixed petroleummaterials are,- as sta te .l, because of their fluidity or their lowmelting or freezing point and non-Volatile nature particularly welladapted for use in making mixed gelatinizaed and plastic explosives,such as nitroglycerin mixtures, n'1ixtures with oxygen-bearing saltssuch as perchlorates, permanganates, chlorates, nitrates, picrates,etc.,

The present process may also be applied. to liquid and easily fusiblephenolic materials, or mixtures of such materials with hydrocarbons;such as acid), the eresols. creosote oils from coal tar, wood tarcreosotes, etc.

1. The process of nitrating organic bodies for the production of!compounds containing two or more nitro f roups wherein such a body in afluid state admixed with a solid nitrate in amount 5n 1 to correspond tothe number of nitrc .xps desired in the product and the mixture soformed is treated with sulfuric acid.

The process of making; permanently liquid. nonwolatile polynitrocompounds of methylated aromatic hydrocarbons which comprises admixingsuch a hydrocarbon in a liquidstate with a solid nitrate in amountssutlicient for the production of-a trinitro compound and thereaftertreating the mixture with sulfuric acid.

The process of 'making; nitro compounds of aromatic h .drocarbons whichcomprisesadmixing such a hydrocarbon in a liquid state with a solidnitrate and thereafter treating the mixture with sulfuricacid.

4. In nitration the process which comprises mixing a liquid organic bodywith a. powdered nitrate to producean intimate mixture and addingsulfuric acid to the mixtureso obtained.

s The w of obtainin polvnitro omare best used as phenol' (carbolic'naphthalene orof mixtures of naphthalene ganic body in a liquid statewith an amo'unt of a solid nitrate more than corresponding to themononitro derivative of such organic body and thereafter treating themixture with sulfuric acid.

6. The process" of obtaining vnitrocornpounds of aromatic-hydrocarbons'oflowered fusing point which comprises admixing a material comprisingsuch aromatic hydrocarbonswith a material'comprising petroleumhydrocarbons, adding the mixture in liquid form to 'a solid nitrate andproducing intimate incorporation and thereafter adding sulfuric acidtd'the 'mixture.

.'Z. In the nitration of tar oils, the process which ciimprises admixingsuch oil with a solid nitrate and thereafter. treating the mix ture withsulfuric acid. 8.,The process of obtaining nitrocompounds of aromatichydrocarbons of lowcred fusing point which fcoinprises admixing amaterialcomprising such aromatic hydrocarbons with a material comprisinganother nitr'atahie organic material, adding the mixture in liquid formto a Solid nitrate and producing'intimate incorporation and thereafteradding sulfuric acid to the mixture.

9. The process of nitration which com-.

prises mixing a solid 'finely powdered nitrate with c-nough'of liquidorganic body to film poa'tfthe' grains thereof and thereafter treatingwith sulfuric acid.

10. 'The'process of nitration which comprises mixing afsolid finelypowdered nitrate with enough, of liquid organic body to film coat thegrains thereof and thereafter'treating-with sulfuric acid at atemperature maintained around 90 C. during the period of' energetic.action.

111- The' process of nitration which comprises inixing solid finely'powdered nitratewith enough of liquid organic body to film coat ,thegranules thereof, treating with sulfuric acid, restraining thetemperature duringthe period of energetic action to a temperaturearoundf90 (1.. and thereafter raising the temperature to expel nitrousfumes.

In testimonywhereof, I afiix my signature. v

E. Rnmon.

